CN110204873A - For the shape memory PCL composite material of 3D printing and its application - Google Patents
For the shape memory PCL composite material of 3D printing and its application Download PDFInfo
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- CN110204873A CN110204873A CN201910308805.5A CN201910308805A CN110204873A CN 110204873 A CN110204873 A CN 110204873A CN 201910308805 A CN201910308805 A CN 201910308805A CN 110204873 A CN110204873 A CN 110204873A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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Abstract
The invention particularly discloses a kind of for the shape memory PCL composite material of 3D printing and its application, belongs to 3D printing field of material technology.Shape memory PCL composite material is grouped as by group as follows as mass fraction: 40~85%PCL, 2~20% high hardness resins, 1%~6% photoinitiator, 0.1%~1% antitack agent, 0.5%~15% photosensitive resin, 0.1%~2% antioxidant and 0%~30% inorganic filler；Difference≤50 DEG C of the fusing point of the fusing point or glass transition temperature and the PCL of the high hardness resin.The present invention mixes light initiation system using free radical-cation, the shape memory PCL composite material for 3D printing is prepared jointly by addition radical photosensitive resin, cationic photosensitive resin, low melting point high hardness resin, antitack agent, antioxidant etc., the three-dimensional structure part printed with the PCL composite wire, it is appropriately crosslinked through ultraviolet light irradiation, three-dimensional structure part not only can effective moulding in 100 DEG C of water, also there is shape memory function, customize medical instrument for 3D printing and open new direction.
Description
Technical field
The invention belongs to 3D printing field of material technology, and in particular to a kind of shape memory PCL for 3D printing is compound
Material and its application.
Background technique
With the continuous development of 3D printing technique, 3D printing material is from initial plastics, photosensitive resin, rubber type of material
Expand to the materials such as metal, ceramics, carbon fiber.In plastic applications, 3D printing consumptive material is still with materials such as PLA, ABS, PA, PETG, TPU
Based on material, with deepening continuously for FDM technology application, industrial auxiliary clamp, medical treatment are slowly penetrated into from initial education sector
The application of guide plate, medical rehabilitation auxiliary instrument etc., especially as the aggravation of Chinese aging, to the need of medical rehabilitation apparatus
It asks more and more, the characteristics of in order to make medical rehabilitation fixture be more suitable for different human body, uses 3D printing customization medical rehabilitation auxiliary
Instrument is increasingly taken seriously；PCL material can be applied to coating in polyurethane resin field, ink, hot melt adhesive, non-woven fabrics bonding
Agent, footwear material, structure glue etc.；Its broader applications operation suture thread, Orthopedic splint, radiotherapy plate, resin in surgical field
Bandage, dental impression etc., it is by extruder extrusion sheet, irradiation that PCL traditional handicraft, which does Orthopedic splint, radiotherapy plate and resin bandage,
It is crosslinked, then is made into the product of manikin structure by plastics suction mould, but general plastic uptake model is limited, and a set of plastic uptake model valence
Lattice are more expensive, and different people, human dimension and structure have difference, this results in the orthopaedics folder being made into traditional handicraft
The products such as plate, radiotherapy plate more or less will appear inadaptability in use, and be to eliminate above-mentioned inadaptability, now pass through
First human body is scanned, constructs the threedimensional model at personal injury position, after carrying out proper treatment to threedimensional model, then passes through 3D
Printing technique comes out three dimensional model printing, so that Orthopedic splint, radiotherapy plate etc. is made to be more suitable for patient, especially patient with severe symptoms,
Inadaptability is reduced, secondary injury is reduced.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of shape for 3D printing
Remember PCL composite material.
Another object of the present invention is to provide the applications of the shape memory PCL composite material for 3D printing.
The purpose of the invention is achieved by the following technical solution:
A kind of shape memory PCL composite material for 3D printing, is grouped as by group as follows as mass fraction: 40~
85%PCL, 2~20% high hardness resins, 1%~6% photoinitiator, 0.1%~1% antitack agent, 0.5%~15% photosensitive tree
Rouge, 0.1%~2% antioxidant and 0%~30% inorganic filler；
Difference≤50 DEG C of the fusing point of the fusing point or glass transition temperature and the PCL of the high hardness resin；The height
Hardness resins are PBAT resin, PE resin, low-melting point PET resin, EVA resin, the pure and mild reduced TG of highly crystalline polyester polyols turn
One of temperature amorphous polyester polyalcohol or at least two mixture；The photoinitiator be 184, TPO, 651,
819,1173,369, luxuriant one of molysite and ITX or at least two mixture；The antitack agent is silicone powder, PE wax, PP
One of wax, stearate, paraffin, EBS and silicone release or at least two mixture；The photosensitive resin is double
Phenol A acrylate, urethane acrylate, polyester acrylate, pure acrylate, HDDA, TMPTA, PETA, NPGDA,
One of DPPA, TPGDA, DPGDA, PDDA, DEGDA and ester ring epoxy resin etc. or at least two mixture.
Preferably, the shape memory PCL composite material is grouped as by group as follows as mass fraction: 50~80%
PCL, 2~13% high hardness resins, 1%~5% photoinitiator, 0.3%~1% antitack agent, 0.5%~14% photosensitive resin,
0.2%~0.8% antioxidant and 0%~28% inorganic filler.
Preferably, the high hardness resin is PBAT resin, low-melting point PET resin, the highly crystalline polyester polyol of low melting point
With one of lower glass transition temperatures polyester polyol or at least two mixtures；The shape memory PCL composite material
There is plasticity in 100 DEG C of water.
Preferably, the photoinitiator is 184, TPO, 651,819,1173,369, luxuriant one of molysite and ITX or extremely
Few two kinds of mixtures.
It is furthermore preferred that the photoinitiator is that photocuring depth can be improved in TPO, 819 or luxuriant molysite, photoinitiator.
Preferably, the antitack agent is in silicone powder, PE wax, PP wax, stearate, paraffin, EBS and silicone release
One kind or at least two mixtures.
It is furthermore preferred that the antitack agent is silicone powder, PE wax, stearate or EBS.
The photosensitive resin be bisphenol A acrylates, urethane acrylate, polyester acrylate, pure acrylate,
One of HDDA, TMPTA, PETA, NPGDA, DPPA, TPGDA, DPGDA, PDDA, DEGDA and ester ring epoxy resin or extremely
Few two kinds of mixtures.
Preferably, the photosensitive resin is the photosensitive resin of degree of functionality >=3 and degree of functionality≤6.
It is furthermore preferred that the photosensitive resin be urethane acrylate, polyester acrylate, pure acrylate, TMPTA,
PETA, PDDA or ester ring epoxy resin.
Preferably, the antioxidant is one of Hinered phenols antioxidant or phosphite ester antioxidant or at least two
Mixture；To reduce influence of the antioxidant to light-cured performance, the preferred phosphite ester antioxidant of the antioxidant or it is low by
Hinder phenolic antioxidant.
The inorganic filler is one of talcum powder, silica, calcium carbonate, barium sulfate, silicon powder or at least two
Mixture；Preferably, the inorganic filler is talcum powder or silica.
It is conventional that the shape memory PCL composite material can be granulated using double screw extruder, single screw rod squeezes out bracing wire etc.
FDM wire rod manufacturing technology be prepared.
The shape memory PCL composite material can be applied in 3D printing, particularly suitable for rehabilitation medical instrument
3D printing, such as the 3D printing of radiation support clamping plate, fixed plate etc..
The shape memory PCL composite material is applied by the following method: the shape memory PCL composite wood is led to
3D printer printer model is crossed, the model is then irradiated by UV, makes the model that there is plasticity when 70-100 DEG C.
The shape memory PCL composite wood is printed into building model, then passes through model described in ultraviolet irradiation, model appropriateness
Crosslinking, crosslink density control are particularly important, it is ensured that model after irradiating in 100 DEG C of water can effective moulding, to ensure model
With certain shape memory function, because 3D printing model is complex-shaped, to prevent non-irradiated position, it is preferable to use freedom
It is uncured to can effectively prevent the non-irradiated position appearance of appearance for base-cationic hybrid ultra-violet curing system.
The present invention has the following advantages and effects with respect to the prior art:
The present invention mixes light initiation system using free radical-cation, by adding radical photosensitive resin, cationic photopolymerization
Quick resin, low melting point high hardness resin, antitack agent, antioxidant etc. are prepared multiple for the shape memory PCL of 3D printing jointly
Condensation material, the three-dimensional structure part printed with the PCL composite wire, appropriately crosslinked through ultraviolet light irradiation, three-dimensional structure part is not
But can in 100 DEG C of water can effective moulding, also have shape memory function, for 3D printing customize medical instrument open new side
To.
Detailed description of the invention
Fig. 1 be using embodiment 1 the PCL composite material with shape memory printed by 3D printer and through surface
Model original graph that treated；
Fig. 2 is figure of the model of Fig. 1 after hot water treatment is redrawn；
Fig. 3 is that the model of Fig. 2 restores the figure of shape after hot water treatment.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Unless otherwise defined, all technical and scientific terms used herein belong to the skill of the technical field of the application
The normally understood meaning of art personnel is identical.Used term is intended merely to description specific embodiment in the description herein
Purpose, it is not intended that in limitation the application.
In the application, in addition to having specified otherwise, all raw materials are commercially available.In the application, word "about" or "approximately" is
Refer in the tolerance interval of the specified design parameter determined by those skilled in the art, be partly dependent on measurement or
Measure the mode of described value, the i.e. limit value of measuring system.For example, " about " can refer to 10% range of at most given value.
In following embodiment, the percentage composition is mass percent.
Embodiment 1
At normal temperatures and pressures, by following component and weight percent: PCL6500 70%, low-melting point PET resin 7%, from
By base photoinitiator 184 1%, cation light initiator 6,990 2%, silicone powder 0.5%, photosensitive resin CY179 3%, photosensitive
It is mixed to carry out high speed in a high speed mixer for resin PETA 2%, phosphite antioxidant 0.5%, inorganic filler talcum powder 14%
10min to be closed, melt blending is carried out using double screw extruder, the modified composite particles of PCL are made in extrusion, pelletizing, drying, packaging,
The modified composite particles single screw rod of PCL is squeezed out into bracing wire again, obtains the shape memory PCL wire rod for 3D printing.
Embodiment 2
At normal temperatures and pressures, by following component and weight percent: the highly crystalline polyester polyols of PCL6500 70%, low melting point
Alcohol 10%, free radical photo-initiation 184 1%, cation light initiator 6,990 3%, silicone powder 0.5%, photosensitive resin CY179
3%, photosensitive resin TMPTA 3%, phosphite antioxidant 0.5%, inorganic filler talcum powder 9%, in a high speed mixer into
Row mixed at high speed 10min carries out melt blending using double screw extruder, and it is modified that PCL is made in extrusion, pelletizing, drying, packaging
Composite particles, then the modified composite particles single screw rod of PCL is squeezed out into bracing wire, obtain the shape memory PCL wire rod for 3D printing.
Embodiment 3
At normal temperatures and pressures, by following component and weight percent: the non-knot of PCL6800 70%, lower glass transition temperatures
Brilliant polyester polyol 10%, free radical photo-initiation 184 1%, cation light initiator 6,990 3%, silicone powder 0.5%, light
Quick resin bis- ((3,4- epoxycyclohexyl) methyl) adipate esters 3%, photosensitive resin PDDA 3%, phosphite antioxidant
0.5%, inorganic filler talcum powder 9% is carried out mixed at high speed 10min in a high speed mixer, is carried out using double screw extruder
Melt blending, extrusion, pelletizing, drying, packaging are made the modified composite particles of PCL, then PCL are modified composite particles single screw rod
Bracing wire is squeezed out, the shape memory PCL wire rod for 3D printing is obtained.
Embodiment 4
At normal temperatures and pressures, by following component and weight percent: PCL6400 30%, 30% reduced TG of PCL6800
Transition temperature non-crystalline polyester polyalcohol 10%, free radical photo-initiation TPO 1%, cation light initiator 6,990 3%, silicon
Ketone powder 0.5%, photosensitive resin bis- ((3,4- epoxycyclohexyl) methyl) adipate esters 4%, photosensitive resin PDDA 4%, phosphorous acid
Ester antioxidant 0.5%, inorganic filler talcum powder 17% carry out mixed at high speed 10min in a high speed mixer, are squeezed using twin-screw
Machine carries out melt blending out, and extrusion, pelletizing, drying, packaging are made the modified composite particles of PCL, then PCL are modified composite particles
Bracing wire is squeezed out with single screw rod, obtains the shape memory PCL wire rod for 3D printing.
Embodiment 5
At normal temperatures and pressures, by following component and weight percent: PCL6800 70%, low melting point crystalline polyester are polynary
Alcohol 10%, free radical photo-initiation TPO 1%, cation light initiator 6,990 3%, silicone powder 0.5%, photosensitive resin are double
((3,4- epoxycyclohexyl) methyl) adipate ester 4%, phosphite antioxidant 0.5%, inorganic is filled out photosensitive resin PDDA 4%
Expect talcum powder 7%, carry out mixed at high speed 10min in a high speed mixer, melt blending is carried out using double screw extruder, is squeezed
Out, pelletizing, drying, packaging are made the modified composite particles of PCL, then the modified composite particles single screw rod of PCL are squeezed out bracing wire, obtain
To the shape memory PCL wire rod for 3D printing.
Comparative example 1
At normal temperatures and pressures, by following component and weight percent: PCL6800 70%, free radical photo-initiation TPO
1%, bis- ((3,4- epoxycyclohexyl) methyl) adipic acids of cation light initiator 6,990 3%, silicone powder 0.5%, photosensitive resin
Ester 4%, photosensitive resin PDDA 4%, phosphite antioxidant 0.5%, inorganic filler talcum powder 17%, in a high speed mixer
Mixed at high speed 10min is carried out, melt blending, extrusion, pelletizing, drying, packaging are carried out using double screw extruder, obtained PCL changes
Property composite particles, then PCL modified composite particles single screw rod is squeezed out into bracing wire, obtains the shape memory PCL line for 3D printing
Material.
Comparative example 2
At normal temperatures and pressures, by following component and weight percent: PCL6800 70%, free radical photo-initiation TPO
1%, silicone powder 0.5%, photosensitive resin PDDA 6%, phosphite antioxidant 0.5%, inorganic filler talcum powder 22%, in height
In fast mixing machine carry out mixed at high speed 10min, using double screw extruder carry out melt blending, extrusion, pelletizing, drying, packaging,
The modified composite particles of PCL are made, then the modified composite particles single screw rod of PCL is squeezed out into bracing wire, obtain the shape for 3D printing
Remember PCL wire rod.
Comparative example 3
At normal temperatures and pressures, by following component and weight percent: PCL6400 30%, PCL6800 30%, low glass
Change transition temperature non-crystalline polyester polyalcohol 10%, free radical photo-initiation TPO 1%, cation light initiator 6,990 3%,
Silicone powder 0.5%, phosphite antioxidant 0.5%, inorganic filler talcum powder 25%, carry out mixed at high speed in a high speed mixer
10min carries out melt blending using double screw extruder, and the modified composite particles of PCL are made in extrusion, pelletizing, drying, packaging, then
The modified composite particles single screw rod of PCL is squeezed out into bracing wire, obtains the shape memory PCL wire rod for 3D printing.
The PCL composite material with shape memory of embodiment 1 is printed by 3D printer and process surface treatment
Model original graph, see Fig. 1；Fig. 2 is figure of the model of Fig. 1 after hot water treatment is redrawn；Fig. 3 is that the model of Fig. 2 passes through
Restore the figure of shape after hot water treatment.
The shape memory PCL wire rod for being used for 3D printing prepared by Examples 1 to 5 and comparative example 1~3 is set with FDM printing
Standby printing threedimensional model, threedimensional model, which is put into, after ultraviolet light solidifies, then to pass through in the ultraviolet light solidification case of 360 degree rotation
Surface treatment is crossed, table 1 is the performance evaluation contrast table of each embodiment and comparative example:
The performance evaluation of table 1 each embodiment and comparative example
The present invention using low melting point high hardness resin improve PCL surface hardness, using FDM machine by threedimensional model parameter into
Row printing, then the model after printing is caused into polymeric photosensitive resin through 360 ° of illumination, make product that there is certain crosslink density,
And PCL surface hardness is further increased, make PCL shaped article that there is shape memory function using the low-density crosslinking of PCL and fusing point
Can, meet the needs of special medical utensil, is pushed further into the application development of FDM technology.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of shape memory PCL composite material for 3D printing, which is characterized in that by component as follows as mass fraction
Composition: 40~85%PCL, 2~20% high hardness resins, 1%~6% photoinitiator, 0.1%~1% antitack agent, 0.5%~
15% photosensitive resin, 0.1%~2% antioxidant and 0%~30% inorganic filler；The fusing point of the high hardness resin or vitrifying
Difference≤50 DEG C of the fusing point of transition temperature and the PCL；
The high hardness resin is that PBAT resin, PE resin, low-melting point PET resin, EVA resin, highly crystalline polyester polyols are pure and mild
One of lower glass transition temperatures amorphous polyester polyalcohol or at least two mixture；The photoinitiator be 184,
TPO, 651,819,1173,369, luxuriant one of molysite and ITX or at least two mixture；The antitack agent is silicone
One of powder, PE wax, PP wax, stearate, paraffin, EBS and silicone release or at least two mixture；The light
Quick resin be bisphenol A acrylates, urethane acrylate, polyester acrylate, pure acrylate, HDDA, TMPTA, PETA,
One of NPGDA, DPPA, TPGDA, DPGDA, PDDA, DEGDA and ester ring epoxy resin etc. or at least two mixing
Object.
2. shape memory PCL composite material according to claim 1, which is characterized in that the shape memory PCL composite wood
Material is grouped as by group as follows as mass fraction: 50~80%PCL, 2~13% high hardness resins, 1%~5% light-initiated
Agent, 0.3%~1% antitack agent, 0.5%~14% photosensitive resin, 0.2%~0.8% antioxidant and 0%~28% inorganic are filled out
Material.
3. shape memory PCL composite material according to claim 1 or 2, which is characterized in that the high hardness resin is
In the pure and mild lower glass transition temperatures polyester polyol of PBAT resin, low-melting point PET resin, the highly crystalline polyester polyols of low melting point
A kind of or at least two mixtures；The shape memory PCL composite material has soft plasticity in 100 DEG C of water.
4. shape memory PCL composite material according to claim 1 or 2, which is characterized in that the photoinitiator be 184,
TPO, 651,819,1173,369, luxuriant one of molysite and ITX or at least two mixtures.
5. shape memory PCL composite material according to claim 1 or 2, which is characterized in that the antitack agent is silicone
One of powder, PE wax, PP wax, stearate, paraffin, EBS and silicone release or at least two mixtures.
6. shape memory PCL composite material according to claim 1 or 2, which is characterized in that the photosensitive resin is function
Degree >=3 and the photosensitive resin of degree of functionality≤6.
7. shape memory PCL composite material according to claim 6, which is characterized in that the photosensitive resin is bisphenol-A third
Olefin(e) acid ester, urethane acrylate, polyester acrylate, pure acrylate, HDDA, TMPTA, PETA, NPGDA, DPPA,
One of TPGDA, DPGDA, PDDA, DEGDA and ester ring epoxy resin or at least two mixtures.
8. shape memory PCL composite material according to claim 1 or 2, which is characterized in that the antioxidant is hindered phenol
One of kind antioxidant or phosphite ester antioxidant or at least two mixture；The inorganic filler is talcum powder, two
One of silica, calcium carbonate, barium sulfate, silicon powder or at least two mixture.
9. shape memory PCL composite material of any of claims 1 or 2 is applied in 3D printing.
10. the application of shape memory PCL composite material according to claim 9, which is characterized in that the shape memory
PCL composite material is applied by the following method: the shape memory PCL composite wood is passed through into 3D printer printer model,
Then the model is irradiated by UV, finally by surface treatment, makes the model that there is plasticity when 70-100 DEG C.
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